CN101677915B - Cosmetic composition comprising fine powder - Google Patents
Cosmetic composition comprising fine powder Download PDFInfo
- Publication number
- CN101677915B CN101677915B CN200880019907.5A CN200880019907A CN101677915B CN 101677915 B CN101677915 B CN 101677915B CN 200880019907 A CN200880019907 A CN 200880019907A CN 101677915 B CN101677915 B CN 101677915B
- Authority
- CN
- China
- Prior art keywords
- powder
- copolymer
- compositions
- phase
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/88—Polyamides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to cosmetic compositions used in the care and makeup field. This composition mainly comprising a continuous aqueous phase, a fatty phase and a pulverulent phase of fine and porous copolyamide powder, is in the form of creamy, liquid or gelled compositions. In particular, an emulsion, but this may also be a two-phase formulation or composition in which the fatty and aqueous phases are separated. The invention more particularly relates to care and/or makeup cosmetic compositions that have a continuous aqueous phase in the case of an oil-in-water emulsion.
Description
The present invention relates to the cosmetic composition used in nursing and cosmetic field.This compositions mainly comprising the powder phase of continuous aqueous phase, fat phase and thin porous copolyamide powder is white shape, liquid state or cementitious compositions form.It is emulsion particularly, but also can be biphase preparation or compositions, wherein fat phase and aqueous phase separation.When oil-in-water emulsion, the present invention relates more specifically to nursing and/or the cosmetic cosmetic composition with continuous aqueous phase.
Surfactant, thickening agent and more generally surfactant (the agents de surface-active) use in emulsion type cosmetic composition of the present invention can obtain phase stabilising dispersions in the other phase.Can also additive be contained in compositions of the present invention, as antiseptic and spice, and cosmetic active agent, as wetting agent (polyhydric alcohol), screening uv-ray agent, anti-wrinkle agent, self-tanning agent, film former, antioxidant etc.
Another theme of the present invention is keratin substances, as cosmetic and/or the nursing of the skin of people, lip, fingernail, hair, eyelashes, eyebrow or chaeta, comprises and compositions of the present invention being applied on keratin substances.
Compositions of the present invention can be cosmetic and/or the nursing compositions of keratin substances, particularly facial-care compositions (such as has frost or the liquid of the character such as moisturizing, crease-resistant and/or makeup removing, and moisturizing and/or biphase washing liquid of removing ornaments and formal dress), body care composition (as moisturizing or slim compositions), waterproof or non-Water-proof sun-proof cream composition, cutization composition for cosmetics, as foundation cream, eye shadow, mascara, kermes, anti-black eye product or health cosmetic product.
From the angle of cosmetics and Galenic formula, continuous water phase type composition has many advantages.They are low cost and use comfortable, because they do not have greasy feeling especially.But their shortcoming is, their denseness is too close to the denseness of water so that do not have captivation to consumer and they have and spread difficulty.In addition, after the moist feeling on skin disappears, they neither improve comfort level, also do not improve maintenance, also do not improve the outward appearance (outward appearance of such as not applying powder) of skin.
Can be addressed these problems by the thickening agent or polyhydric alcohol that add generation denseness in the formulation.But due to being clamminess of being caused by the existence of polyhydric alcohol, even sticky effect, this series products makes said preparation be difficult to spread usually.In addition, these additives leave glossy effect after spreading on skin, and may block skin pore.
In document EP1582194, describe the cosmetic composition of powder comprising liquid, cream frost or powder binder, spice and formed by spherical, cylindrical or dumb-bell shape polyamide (being abbreviated as PA) particle.These particles are porous, have the ratio of the average diameter of 1 to 30 micron, 5 meters squared per gram or larger specific surface area, 200 milliliters/100 grams or larger linseed oil absorption, the degree of crystallinity of 40% or higher and the volume mean diameter of 1.0 to 1.5 and number average diameter.Homopolyamide 12 or 6 powder of these compositionss causes light scattering effect on a skin surface and has high sebum absorbing ability, and this is effectively reduced in the abnormal luminous reflectance produced on skin when described compositions being applied on skin.
In addition, in described document EP1582194, an embodiment shows, homopolyamide 6 powder (when they are introduced foundation cream) made as described in this article produces when spreading and causes the organoleptic properties of plump sense class to be better than the organoleptic properties of homopolyamide 12 powder.
But, observe after research work, the polyamide powder described in the prior art can not solve the problem run into for the compositions with continuous aqueous phase: in fact, although the plump sense that the homopolyamide 6 powder denseness that greatly raising has the preparation of continuous aqueous phase is expected to give user when spreading, they do not produce soft feeling after preparation spreads.
On the contrary, the denseness of homopolyamide 12 powder on the preparation with continuous aqueous phase does not almost affect.Although with the addition of polyamide powder, these preparations still keep user not to be the denseness of the water appreciated very much.On the other hand, the sensation stayed after spreading on skin is very soft.
Having been found that by using copolyamide powder, can prepare and give plump sense that described compositions expects with user and after spreading, leave the compositions with continuous aqueous phase that soft face powder feels.
A theme of the present invention is a kind of compositions, it comprises (i) aqueous phase, (ii) fatty phase, and (iii) comprises the powder phase of the copolyamide powder generated by least two kinds of different following monomers and other polymerization at undefined compound optional.This compositions can be have the emulsion of continuous aqueous phase (oil-in-water) or have the two-phase compositions of aqueous phase separately and fatty phase.
Continuous aqueous phase of the present invention can comprise thickening agent, emollient, wetting agent (humectants) (as polyhydric alcohol) and/or wetting agent (hydratants).
Fat of the present invention can comprise plant, mineral, animal mutually or synthesize solid or the liquid fatty substance in source.Such as ester, fatty alcohol, fatty acid can be mentioned, substantially comprise carbon and hydrogen atom and optionally comprise the hydrocarbon of nitrogen or oxygen atom.Also silicone oil and fluorinated oil can be mentioned.
According to an embodiment, the feature of said composition is, this powder particle has 1 micron to 200 microns, preferably 1 to 100 micron, more preferably 1 to 50 micron, then the average diameter of more favourable 1 to 20 micron, the specific surface area of 1 to 25 meters squared per gram and spherical.
According to an embodiment, the feature of said composition is that it comprises (relative to % by weight of total composition):
59.9 to 98.9%, the preferably aqueous phase of 69 to 95%;
0.1 to 30%, the preferably powder phase of CoPA powder of 1 to 20%; With
The fatty phase of 40 to 1%.
According to an embodiment, the feature of said composition is, this aqueous phase comprises the polyhydric alcohol of 1 to 99% (relative to % by weight of total composition), preferably 10 to 60%.
According to an embodiment, the feature of said composition is, it comprises at least one and is selected from antioxidant, spice, antiseptic, nertralizer, surfactant, film forming polymer, thickening agent, screening uv-ray agent, vitamin, coloured material, emulsion stabilizer, wetting agent, cosmetic composition from tanned compound, antiwrinkle active agent and composition thereof.
According to an embodiment, the feature of said composition is, it is moisturizing, the face nursing care cream of crease-resistant and/or makeup removing or liquid, moisturizing and/or slim body care frost or liquid, waterproof or non-watertight sunscreen, foundation cream, eye shadow, mascara, kermes, anti-black eye product or health cosmetic product, biphase moisturizing or makeup removing liquid.
The invention still further relates to the cosmetic of compositions for the manufacture of skin and/or the purposes of care product, this product give after being applied on described skin skin emolliency sense and sub-light face powder outward appearance.
The invention still further relates to the cosmetic of keratin substances and/or the cosmetic method of nursing, be included on these materials and spread compositions as above.
According to an embodiment, the feature of the purposes of this thin voluminous powder is, this powder particle has the average diameter of 5 to 10 microns.
According to an embodiment, the feature of the purposes of this thin voluminous powder is, this powder particle has spherical.
In more detail the present invention is described now.
powder
About copolyamide powder (being abbreviated as CoPA powder), be interpreted as the condensation product referring at least two kinds of different monomers, described monomer is selected from:
-amino acid type monomers;
-there are 3 to 12 carbon atoms on main ring and the lactams type monomer that can be substituted;
-the monomer that generated by the reaction that has between the aliphatic diamine of 6 to 12 carbon atoms and the dicarboxylic acids with 4 to 18 carbon atoms; With
-their mixture, when mixture between amino acid type monomers and lactams type monomer, monomer has different carbon number.
As the example of lactams, can mention there are 3 to 12 carbon atoms on main ring and can be substituted those.Such as can mention β, beta-dimethyl-azetidinone (β, β-dim é thylpropriolactam), α, alpha-alpha-dimethyl azetidinone (α, α-dim é thylpropriolactam), valerolactam (amylolactam), caprolactam, spicy inner formyl amine, oenantholcatam, 2-Pyrrolidone and lauryl lactan (lauryllactame).
As the example of dicarboxylic acids, the acid with 4 to 18 carbon atoms can be mentioned.Such as can mention adipic acid, decanedioic acid, Azelaic Acid, suberic acid, M-phthalic acid, succinic acid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid, p-phthalic acid, the sodium of sulfoisophthalic acid or lithium salts, dimer (fatty acid) yl (these dimer (fatty acid) yls have the dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC-(CH
2)
10-COOH.
As the example of diamidogen, it can be the aliphatic diamine with 6 to 12 carbon atoms, and it can be saturated aryl diamine and/or cyclic diamine.Such as, hexamethylene diamine, piperazine, butanediamine, octamethylenediamine, decamethylene diamine, dodecamethylene diamine, 1 can be mentioned, 5-diamino hexane, 2,2,4-trimethyl-1，6-diaminohexane, two amine polyols, isophorone diamine (IPD), making methylpentamethylenediamine diamine (MPDM), two (aminocyclohexyl) methane (BACM), two (3-methyl-4-aminocyclohexyl) methane (BMACM), m-xylene diamine, bis(p-aminocyclohexyl)methane and trimethylhexane diamine.
When synthesizing CoPA by lactams by anionic route, the method is lactams to be suspended in organic liquid or is dissolved in a solvent and carry out anionic polymerization, this polymerization can directly obtain CoPA powder, and it is separated with liquid medium automatically when being formed.The anionic polymerization method of lactams is substantially based on using catalyst (as one of sodium or its compound; as sodium hydride or Feldalat NM) and activator (especially as imines and the ester of lactams-carboxyailine, isocyanates, carbodiimide, cyanogen imines (cyanimides), acyl lactam, triazine, urea, N-replacement); especially optionally playing the in small, broken bits inorganic or organic filler of crystal seed effect, as PA powder (such as
powder), under silicon dioxide powder or Pulvis Talci exist, and at N, N '-alkylidene bisamide, particularly N, N '-ethylenebisstearamide, N, N '-ethylenebisoleoamide, N, N '-ethylenebis palmitamide, gadol é amide, c é tol é amide, é rucamide, N, N '-diol é yldipamide and N, under N '-two mustard amide exists.The method is described in patent EP192 515 and EP303 530.
Can mention by least two kinds of α, omega-amino-carboxylic acid or two kinds of lactams or a kind of lactams and a kind of α, the copolyamide that the condensation of omega-amino-carboxylic acid produces.As α, the example of omega-amino acid, can mention aminocaproic acid, 7-aminoheptylic acid, 11-amino undecanoic acid and 12 amino dodecanoic acid.Also can mention by least one α, the copolyamide of the condensation generation of omega-amino-carboxylic acid (or lactams), at least one diamidogen and at least one dicarboxylic acids.Also can mention by other be selected from and aforementioned different aliphatic diamine and the copolyamide that produces with the condensation of the monomer of aforementioned different aliphatic diacid of aliphatic diamine and aliphatic dicarboxylic acid and at least one.
As the example of copolyamide, the copolymer (PA6/12) of caprolactam and lauryl lactan can be mentioned, caprolactam, the copolymer (PA6/6-6) of adipic acid and hexamethylene diamine, caprolactam, lauryl lactan, the copolymer (PA6/12/6-6) of adipic acid and hexamethylene diamine, caprolactam, lauryl lactan, 11-amino undecanoic acid, the copolymer (PA6/6-9/11/12) of Azelaic Acid and hexamethylene diamine, caprolactam, lauryl lactan, 11-amino undecanoic acid, the copolymer (PA6/6-6/11/12) of adipic acid and hexamethylene diamine, lauryl lactan, the copolymer (PA6-9/12) of Azelaic Acid and hexamethylene diamine, the copolymer (PA4/6) of 2-Pyrrolidone and caprolactam, the copolymer (PA4/12) of 2-Pyrrolidone and lauryl lactan, the copolymer (PA6/11) of caprolactam and 11-amino undecanoic acid, the copolymer (PA12/8) of lauryl lactan and spicy inner formyl amine, the copolymer (PA11/4) of 2-Pyrrolidone and 11-amino undecanoic acid, the copolymer (PA8/6) of caprolactam and spicy inner formyl amine, the copolymer (PA8/4) of 2-Pyrrolidone and spicy inner formyl amine, and the copolymer of lauryl lactan and spicy inner formyl amine (PA12/8).
Polyamide and/or copolyamide mixture can be used.These are mixture of such as aliphatic polyamide and partially aromatic polyamide, and the mixture of aliphatic polyamide and alicyclic polyamide.
Can be made powder by any mode (being dissolved in alcohol neutralization to precipitate from alcohol).Advantageously, by being polymerized in a solvent, make powder, this powder is insoluble in this solvent (anionic polymerization defined above).The method described in EP192515 and EP303530 can be mentioned.
Also the copolyesteramide powder produced by the condensation of llowing group of materials (total amount 100%) can be used:
1 to 98 % by mole of lactams;
1 to 98 % by mole of lactone; Optionally
1 to 98 % by mole from aforementioned other different lactams.
The lactams that can be used for manufacturing copolyesteramide is with mentioned above those are identical.Advantageously, lactams and lauryl lactan is used.As the example of lactone, caprolactone, valerolactone and butyrolactone can be mentioned.Advantageously, caprolactone is used.
When copolyesteramide, caprolactam, lauryl lactan and caprolactone advantageously use with following respective ratio (% by mole): 30-46%, 30-46% and 8-40% (total amount is for 100%).
The method being prepared these copolyesteramide powder by anionic polymerization is described in EP1172396.
fat phase
Fat can contain liquid aliphatic phase and optional hard fat phase (as wax) mutually.Liquid aliphatic can be the oil of liquid mutually containing one or more under room temperature (25 DEG C), and these oil are volatility or nonvolatile.Liquid aliphatic is formed by hydrocarbon-base oil or even optional silicone oil.
This fat comprises one or more oil mutually, i.e. the immiscible fatty material with water.These volatility or nonvolatile oil are mineral, animal, plant or synthesis source, and can be hydrocarbon-Ji, organosilicon-Ji or fluorinated oil.Term " hydrocarbon-base oil " is understood to mean basically, by carbon and hydrogen atom and optional oxygen or nitrogen-atoms is formed or the oil that is even made up of them.It can contain alcohol, ester, ether, carboxylic acid, amine and/or amide group.
It can be the oil of liquid containing one or more under room temperature (25 DEG C), preferred at least one non-volatile liquid oil.Term " non-volatile liquid oil " is understood to mean and can stops on skin under room temperature (25 DEG C) and atmospheric pressure at least 1 hour and have the oil being less than or equal to the non-zero vapor pressure of 0.01mmHg (1.33Pa) under room temperature (25 DEG C) and atmospheric pressure especially.
This liquid aliphatic advantageously comprises the nonvolatile oil that one or more provide skin moistening effect on skin mutually.Fatty ester can be mentioned, as different n-nonanoic acid 16-octadecane ester, the different tridecane ester of different n-nonanoic acid, isostearic acid octadecane ester, IPIS, isopropyl myristate, isopropyl palmitate, butyl stearate, lauric acid hexyl ester, isononyl isononanoate, Palmic acid 2-Octyl Nitrite, lauric acid 2-hexyl ester in the last of the ten Heavenly stems, Palmic acid 2-octyl group ester in the last of the ten Heavenly stems, myristic acid or lactic acid 2-octyldodecyl ester, succinic acid two (2-Octyl Nitrite), malic acid two isooctadecane ester, three glyceryl isostearates or triglyceride, tocopherol acetas; Higher fatty acids, as myristic acid, Palmic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid, caprylic/capric triglyceride; High fatty alcohol, as oleyl alcohol; American Avocado Tree oil, Camellia oil, macadimia nut oil, turtle oil, mink oil, soybean oil, Oleum Vitis viniferae, Oleum sesami, Semen Maydis oil, Oleum Brassicae campestris, sunflower oil, Oleum Gossypii semen, Jojoba oil, Oleum Arachidis hypogaeae semen, olive oil, lauric acid hexyl ester and composition thereof.
They can be mineral oil, hydrocarbon-base oil, as liquid paraffin, squalane, vaseline oil and composition thereof.
Said composition optionally comprises non-volatile silicone oil, as dimethyl siloxane.
This liquid aliphatic optionally can also comprise ethereal oil mutually.Term " ethereal oil " is understood to mean the oil that can evaporate from skin in lower than 1 hour at room temperature and atmospheric pressure.This oil has especially and under room temperature (25 DEG C) and atmospheric pressure (760mmHg), is greater than 0.01 and is less than or equal to 300mmHg (1.33Pa to 40000Pa), the preferably vapour pressure of 0.05 to 300mmHg (6.65Pa to 40000Pa).
Ethereal oil is such as selected from the silicone oil of the greasy effect contributing to alleviating the preparation with continuous fatty phase.Can mention and have line style or the cyclic silicone oils that the viscosity being at room temperature less than 8 square millimeters/second also especially has 2 to 7 silicon atoms, these silicone oil optionally comprise the alkyl and alkoxyl with 1 to 10 carbon atom.As volatile silicone oils available in the present invention, octamethylcy-clotetrasiloxane (actam é thyl cyclot é trasiloxane), decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, seven methylhexyl trisiloxanes, seven Methyl Octyl trisiloxanes, hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, ten dimethyl five siloxanes and composition thereof can be mentioned especially.
They are particularly selected from poly-alkylsiloxane and poly-polty (arylsiloxane) alkanes: Cyclomethicone (DC345 from Dow Corning), caprylyl polydimethylsiloxane, D5 (DC245 from Dow Corning).
Also volatile hydrocarbon-based oil with 8 to 16 carbon atoms and composition thereof can be mentioned, especially side chain C8 to C16 alkane, as C8 to C16 isoalkane (also referred to as isoparaffin), Fancol ID, isodecane, 2-Methylpentadecane, side chain C8 to C16 ester, as isohexyl neopentanoate ester and composition thereof.
aqueous phase
This aqueous phase contains water.The latter can be Hua Shui, as Centaurea cyanus water and/or mineral water, as the water from Vittel, the water from Lucas or from the water of La Roche Posay and/or thermal water (eau thermale).This aqueous phase can also comprise water miscibility composition, as primary alconol, as ethanol and isopropyl alcohol, polyhydric alcohol, glycol as added due to its moisturizing character: glycerol, propylene glycol, butanediol, dipropylene glycol, diethylene glycol, glycol ether, as single-, two-or tripropylene glycol or single-, two-or (C1-C4) alkyl ether of triethylene glycol, and composition thereof.
This aqueous phase can also comprise stabilizing agent, as sodium chloride, magnesium dichloride and magnesium sulfate.
This aqueous phase can also comprise any water solublity compatible with aqueous phase or dispersible compounds, as gellant, film forming polymer, thickening agent, surfactant and composition thereof.
other compound
Cosmetic composition of the present invention can also comprise the dispersion of promotion fat in aqueous phase to obtain the anionic of stable oil/water emulsion, nonionic or amphoteric surfactant (normally lipophilic), additive is as antiseptic (usually hydrophilic), spice (usual lipophilic), be different from the filler of powder of the present invention, coloured material (soluble dye, pigment), thickening agent (wax, gellant), emulsion stabilizer (usually hydrophilic) or chelating agen (usually hydrophilic).
Surfactant can be esters type, as sorbitan acid anhydride derivant (such as sorbitan acid anhydride sesquialter isostearate) or methyl glucoside isostearate.They can be polymer types, as PEG-45/ dodecanediol copolymer.They also can be the organic silicon surfactants being applicable to emulsified silicone oil: they are such as dimethicone copolyols, as Dow Corning with DC5225C run after fame sell PEG/PPG-18/18 polydimethylsiloxane.
Thickening agent such as can dissolve in fat to regulate its denseness or to contribute to the stability of said composition: can mention such as, candelilla wax, silicone rubber or elastomer (DC1411 and DC9040 from Dow Corning).
Antiseptic is the mixture of para-hydroxybenzoic acid esters derivatives and/or phenyl phenol.
Can mention such as ethylenediaminetetraacetic acid (EDTA) as chelating agen.
It also can comprise the cosmetic active agent improving above-mentioned human keratin materials.Cosmetic active agent comprises wetting agent (usually hydrophilic, as polyhydric alcohol), ultraviolet radiation screening agent (as Orangic sunscreen (usual lipophilic) or mineral particle, as warp or not surface treated Ti0
2or ZnO), anti-wrinkle agent (usually hydrophilic), self-tanning agent (usually hydrophilic), film former (according to their character, lipophilic or hydrophilic) or antioxidant (according to their character, lipophilic or hydrophilic).
As inorganic sunscreen, the dispersion of ZnO and Ti02 in silicon oil mixture can be mentioned.
With regard to it, aqueous phase preferably comprises relative to total aqueous phase 1 to 99 % by weight, preferably the polyhydric alcohol of 10 to 60 % by weight.
In addition, it can comprise relative to total composition 0.5 to 10%, preferably the surfactant of 3 to 5%, the additive of 0.01 to 2% and 0.005 to 10% cosmetic active agent.
Feature as the CoPA powder of the compositions of one of theme of the present invention is:
The average diameter of particle is 0.1 to 100 micron, preferably 0.5 to 50 micron, more favourable 1 to 20 micron.
Narrow particle size distribution.According to common technology, such as, use Coulter Multisizer II particle size analyzer, measure the particle size distribution of powder according to standard ISO 13319.Use this particle size distribution, can measure average diameter and granularity discrete (standard deviation), it measures narrowing of this distribution.One of advantage of described method is that can to obtain standard deviation be 1 to 3 micron or is even usually less than the narrow ditribution of 2 microns;
Particle favourable spherical, i.e. spherical form, this refers to: roughly spherical solid.
Above-listed feature greatly contributes to having the soft feeling in the system of continuous aqueous phase and contributes to obtaining the face powder outward appearance (aspect mat et poudr é) of sub-light of said composition after spreading.
These features also give the character occurred as the wrinkle in the powder minimizing skin surface of theme of the present invention or flaw.
Specify the embodiment in following table 1 to 4 in the following manner:
powder 1:
2002EXD NAT COS, i.e. PA12 powder, average particle diameter=10 micron, SSA=4 ± 1.5 meters squared per gram, the Semen Lini oil meltage (prise) of 79 grams/100 grams, obtains according to the method described in EP192515.
powder 2: be crystal seed with copolyamide PA12/PA6 (80/20) powder
particle size=10 micron, SSA=9.5 ± 1 meters squared per gram
To keeping introducing in reactor under a nitrogen: 2800 milliliters of solvents, then in succession introduce 108 restrain oneself lactams, 679 grams of dry lauryl lactans, 14.4 grams EBS and 112 gram in small, broken bits
2001UD NAT1.After start stirring with 300rpm, this mixture is heated to 110 DEG C gradually, then distills 290 milliliters of solvents under vacuo to be distillated the trace water that may exist by azeotropic.
Recover after atmospheric pressure, introduce rapidly anionic catalyst subsequently under a nitrogen and in oil with 7.2 of 60% purity grams of sodium hydrides, and at 110 DEG C, stirring is increased to 720rpm30 minute under a nitrogen.
Then, cool the temperature to 96 DEG C, and by little dosing pump, according to follow procedure by selected activator, namely Carbimide. octadecane ester (32.9 grams, by solvent make-up to 314 gram) injects reaction medium continuously:
10 Grams Per Hour isocyanate solutions, 300 minutes periods; With
88 Grams Per Hour isocyanate solutions, 180 minutes periods;
Abreast, make temperature first keep at 96 DEG C first 360 minutes, then in 60 minutes, rise to 110 DEG C, and at 110 DEG C, keep 2 hours again after introducing isocyanates.
Then stop polymerization, reactor is almost clean.After being cooled to 80 DEG C, decantation and drying, granularity is 2 to 20 microns, and average particle diameter is 11.8 microns, and SSA is 9.3 meters squared per gram, without aggregation.
powder 3:
3502D NAT1, copolyamide PA12/PA6 (50/50) powder, average particle diameter=20 micron, SSA=2.5 ± 1 meters squared per gram.
powder 4: copolyamide PA12/PA6 (50/50) powder, average particle diameter=10 micron, SSA=20 ± 1 meters squared per gram, obtains according to the method described in EP192515.
powder 5:
3202D NAT1, copolyamide PA12/PA6 (20/80) powder, average particle diameter=20 micron, SSA=1 ± 1 meters squared per gram.
powder 6:
1002D NAT COS, copolyamide PA6 powder, average particle diameter=20 micron, SSA=1 ± 1 meters squared per gram.
contrastcompositions does not conform to powder.
Following percentage ratio represents with weight relative to total composition.For each table, definition below comprises the character of the compositions of powder 1 to 6.
Measured the effect adding PA powder of the present invention in the emulsion with continuous aqueous phase by organoleptic analysis in various types of compositions.Each compositions is the object of the sense organ situation research undertaken by five panels of expert according to following specifications:
-spread in the stage at product: enrichment (richesse), seepage velocity; With
-after just spreading: the powder that skin oil luminosity (brillant), skin emolliency degree, said composition stay on skin remains
By comparing the serial all tests of formation one under blinded conditions, analyze each compositions.
Result is organized in table 1 to 4.With 0 to 8 for scale, evaluate and test various standard.Numerical value 0 refers to the standard (such as, there is not soft feeling) not existing and specify; Numerical value 8 refer to for the obviously trend (such as, high soft feeling) selecting standard.
Compositions A to F and tester 1 are the oil-in-water emulsion type compositionss comprising 5% fatty phase, are equivalent to the compositions of such as clear (1 é geres) frost.
The method preparing following compositions is that (1) merges and heating aqueous phase A to 75 DEG C, (2) merging and heating fat phase (B) are to 75 DEG C, (3) fatty phase B is slowly added in phase A to form emulsion while vigorous stirring, then (4) are cooled to room temperature, then under agitation add the composition of phase C, then add while gentle agitation powder (phase D) (except tester).
tester 1: x=0% powder
compositions A: x=3.5% powder 1
compositions B: x=3.5% powder 2
compositions C: x=3.5% powder 3
compositions D: x=3.5% powder 4
compositions E: x=3.5% powder 5
composition F: x=3.5% powder 6
Table 1
compositions G to L in table 2 and tester 2 are the oil-in-water emulsion type compositionss comprising 10% fatty phase, can be equivalent to such as moisturizing day cream, are called moist type frost.
The method preparing following compositions is that (1) merges and heating aqueous phase A to 75 DEG C, (2) merging and heating fat phase B to 75 DEG C, (3) fatty phase B is slowly added in phase A to form emulsion while vigorous stirring, then (4) are cooled to room temperature, then under agitation add the composition of phase C, then add while gentle agitation powder (phase D) (except tester).
tester 2: x=0% powder
compositions G: x=3.5% powder 1
compositions H: x=3.5% powder 2
composition I: x=3.5% powder 3
compositions J: x=3.5% powder 4
compositions K: x=3.5% powder 5
compositions L: x=3.5% powder 6
Table 2
By 0.2 % by weight to 30 % by weight, preferably 0.5 % by weight to 10 % by weight CoPA powder adds in oil-in-water emulsion (especially nursing type after day cream, moisture retention liquid, body lotion or palpus) can provide enrichment for said preparation, and this is associated with denseness.In addition, after spreading, the use of this copolyamide powder can give the soft feeling that skin obtains far above pure PA powder.Finally, after spreading, said preparation leaves powder and remains on skin, and this scattered light also covers flaw.This powder add can obtain sub-light, the outward appearance of smooth, nature and face powder shape.
Especially, in the tester 1 type compositions containing a small amount of fatty phase, the interpolation of CoPA powder significantly improves the denseness of this frost and it can be made to leave the impression of enrichment to user, and can not produce the oiliness compound causing greasy feeling.After spreading, produce more soft sensation and more significant powder containing the CoPA powder more than 20 % by mole of PA12 residual.
Especially, in the tester 2 type compositions containing greater amount fat phase, the interpolation of CoPA powder significantly improves the denseness of this frost and it can be made to leave the impression of enrichment to user, and can not produce the oiliness compound causing greasy feeling.After spreading, produce more soft sensation containing the CoPA powder more than 50 % by mole of PA12, more significant powder remains and higher smoothing effect.
compositions M to N in table 3 and tester 3 are the oil-in-water emulsion type compositionss comprising 15.5% fatty phase.These compositionss are equivalent to such as anti-wrinkle cream preparation.
tester 3: x=0% powder
compositions M: x=3.5% powder 1
compositions N: x=3.5% powder 2
The method preparing following compositions is that (1) merges and heating aqueous phase A to 75 DEG C, (2) merging and heating fat phase B to 75 DEG C, (3) fatty phase B is slowly added in phase A to form emulsion while vigorous stirring, then (4) add C (pH=6.9) after following this emulsifying closely, then (5) are cooled to 60 DEG C, then D is added, then (6) are cooled to room temperature, then add the composition of phase E, then (7) add powder (phase F) (except tester) while gentle agitation.
Table 3
What characterize in table 3 comprises in the oil-in-water emulsion type preparation of 15.5% fatty phase, and this copolyamide provides much more excellent than pure polyamide PA12 powder pliability and powder to remain.
In addition, measured the smoothing effect of compositions N by fringe projection method (m é thode de projection de frange), its principle is as follows: for 20 healthy women objects, measures skin rise and fall at crows-feet place by fringe projection.
Fringe projection technology can confirm the change of the skin pattern of crows-feet.The optical system being exclusively used in tolerance surface undulation is used to carry out this measurement.
This system comprises the sensor being connected to projector and being connected on high resolution CCD photographing unit.Average axis and lateral resolution are about 10 microns.
By calculating standard roughness parameter, carry out the analysis of skin surface pattern.Obtain these parameters from the region being measured as 30 × 40 millimeters (12 square centimeters), represent with millimeter.
The parameter of quantification is the acquisition on a series of profiles vertical with microgroove with the wrinkle of relevant range.
Such as, get parms SPt (the most high-amplitude of fluctuating).For crows-feet, the reduction of SPt means alleviating of main wrinkle.
Preparation N causes SPt parameter to reduce by 4% after this product being applied to crows feet area upper 20 minute, reduces by 6% after 2 hours.
This result is equivalent to from spreading after this product in the of 20 minutes, roughness parameter SPt (fluctuating most high-amplitude) significantly reduces (in whole plane average-4%), and be confirmed and strengthen (in whole plane on average-6%) for 2 hours after spreading.This significant change means that the degree of depth of the main wrinkle of crows-feet reduces.
compositions O to P in table 4 and tester 4 are the oil-in-water emulsion type compositionss comprising 26.5% fatty phase.These compositionss are equivalent to the sunscreen cream preparation such as with high SPF (sun protection factor).
For this kind of preparation, in the sensory study being particularly useful for the sun-screening agent with high SPF (sun protection factor), add another specification: the white produced by sunscreen namely observed after spreading remains.When not staying white residual after spreading said preparation on skin, this specification is cited as 0; Stay on skin after spreading a large amount of white residual time, it is cited as 8.
The method preparing following compositions is that (1) merges and heating aqueous phase A to 70 DEG C, (2) merging and heating fat phase B to 70 DEG C, (3) fatty phase B is slowly added in phase A to form emulsion while vigorous stirring, then (4) are cooled to room temperature, then the composition of phase C, then (5) under agitation add phase D, and then (6) add powder (phase E) (except tester) while gentle agitation.
tester 4: x=0% powder
compositions O: x=5% powder 1
compositions P: x=5% powder 2
Table 4
What characterize in table 4 comprises in the oil-in-water emulsion type preparation of 26.5% fatty phase, and this copolyamide provides much more excellent than pure polyamide PA12 powder pliability and powder to remain; They significantly reduce the effect that bleaches of this sunscreen.
Claims (15)
1. cosmetic composition, it comprises, relative to % by weight of total composition:
The aqueous phase of 69 to 95%, wherein aqueous phase comprises thickening agent, emollient, wetting agent and/or wetting agent;
The powder phase comprising the copolyamide powder being polymerized generation by least two kinds of different monomers of 1 to 20%; With
The fatty phase of 40 to 1%, wherein fat comprises plant, mineral, animal mutually or synthesizes solid or the liquid fatty substance in source, and described compositions is the two-phase compositions that oil-in-water emulsion or its aqueous phase are separated with fat,
Wherein this copolyamide is selected oneself the copolymer (PA 6/12) of lactams and lauryl lactan, caprolactam, the copolymer (PA 6/6-6) of adipic acid and hexamethylene diamine, caprolactam, lauryl lactan, the copolymer (PA 6/12/6-6) of adipic acid and hexamethylene diamine, caprolactam, lauryl lactan, 11-amino undecanoic acid, the copolymer (PA 6/6-9/11/12) of Azelaic Acid and hexamethylene diamine, caprolactam, lauryl lactan, 11-amino undecanoic acid, the copolymer (PA6/6-6/11/12) of adipic acid and hexamethylene diamine, lauryl lactan, the copolymer (PA 6-9/12) of Azelaic Acid and hexamethylene diamine, the copolymer (PA4/6) of 2-Pyrrolidone and caprolactam, the copolymer (PA4/12) of 2-Pyrrolidone and lauryl lactan, the copolymer (PA6/11) of caprolactam and 11-amino undecanoic acid, the copolymer (PA12/8) of lauryl lactan and spicy inner formyl amine, the copolymer (PA11/4) of 2-Pyrrolidone and 11-amino undecanoic acid, the copolymer (PA8/6) of caprolactam and spicy inner formyl amine, the copolymer (PA8/4) of 2-Pyrrolidone and spicy inner formyl amine, and the copolymer of lauryl lactan and spicy inner formyl amine (PA12/8).
2., according to the compositions of aforementioned claim, it is characterized in that the particle of this copolyamide powder has spherical and 1 micron to 200 microns average diameter.
3. compositions according to claim 2, is characterized in that the particle of this copolyamide powder has the average diameter of 1 to 100 micron.
4. compositions according to claim 2, is characterized in that the particle of this copolyamide powder has the average diameter of 1 to 50 micron.
5. compositions according to claim 2, is characterized in that the particle of this copolyamide powder has the average diameter of 1 to 20 micron.
6. compositions according to claim 2, is characterized in that the particle of this copolyamide powder has the specific surface area of 1 to 25 meters squared per gram.
7. compositions according to claim 1, it is characterized in that this aqueous phase comprise relative to total aqueous phase 1 to 99 % by weight polyhydric alcohol.
8. compositions according to claim 7, it is characterized in that this aqueous phase comprise relative to total aqueous phase 10 to 60 % by weight polyhydric alcohol.
9. compositions according to claim 1, is characterized in that it also comprises relative to total composition % by weight:
The surfactant of 0.5 to 10%;
The additive of 0.01 to 2%; With
The cosmetic active agent of 0.005 to 10%.
10. compositions according to claim 9, is characterized in that it comprises, relative to the surfactant of % by weight, 3 to 5% of total composition.
11. compositionss according to claim 9, is characterized in that this additive is selected from antiseptic, spice, the filler being different from copolyamide powder, coloring material, thickening agent, emulsion stabilizer and chelating agen.
12., according to the compositions of claim 9 or 11, is characterized in that this cosmetic active agent is selected from wetting agent, screening uv-ray agent, anti-wrinkle agent, self-tanning agent, film former and antioxidant.
13. compositionss according to claim 1, is characterized in that it is moisturizing, the face nursing care cream of crease-resistant and/or makeup removing or liquid, moisturizing and/or slim body care frost or liquid, waterproof or non-watertight sunscreen cream, foundation cream, eye shadow, mascara, kermes, anti-black eye product or health cosmetic product, biphase moisturizing or makeup removing washing liquid.
14. according to the cosmetic of compositions for the manufacture of skin of aforementioned any one of claim and/or the purposes of care product, and this product to give skin with the face powder outward appearance of soft feeling and sub-light being applied to after on described skin.
The cosmetic of 15. keratin substances and/or the cosmetic method of nursing, be included in the compositions these keratin substances spread according to any one of claim 1 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0754431A FR2914856B1 (en) | 2007-04-12 | 2007-04-12 | COSMETIC COMPOSITION COMPRISING A FINE POWDER |
| FR0754431 | 2007-04-12 | ||
| PCT/FR2008/050662 WO2008145889A2 (en) | 2007-04-12 | 2008-04-14 | Cosmetic composition comprising a fine powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101677915A CN101677915A (en) | 2010-03-24 |
| CN101677915B true CN101677915B (en) | 2015-05-20 |
Family
ID=38752554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880019907.5A Active CN101677915B (en) | 2007-04-12 | 2008-04-14 | Cosmetic composition comprising fine powder |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US10463889B2 (en) |
| EP (1) | EP2134313A2 (en) |
| JP (1) | JP5551580B2 (en) |
| KR (1) | KR101516444B1 (en) |
| CN (1) | CN101677915B (en) |
| AU (1) | AU2008257296A1 (en) |
| BR (1) | BRPI0810537B1 (en) |
| FR (1) | FR2914856B1 (en) |
| MX (1) | MX336952B (en) |
| RU (1) | RU2009141710A (en) |
| WO (1) | WO2008145889A2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008051007A1 (en) | 2008-10-13 | 2010-04-15 | Beiersdorf Ag | Polyamide-5 compounds in cosmetic preparations |
| FR2962042B1 (en) * | 2010-07-01 | 2013-02-08 | Arkema France | COSMETIC COMPOSITION COMPRISING COPA. |
| EP2680818B1 (en) | 2011-03-02 | 2017-11-29 | Deb IP Limited | Chemical composition with hydrogen peroxide and a nanoemulsion of long-chained alcohols |
| FR2979235B1 (en) * | 2011-08-26 | 2015-04-03 | Lvmh Rech | MASCARA IN THE FORM OF POWDER |
| KR101584410B1 (en) * | 2013-12-04 | 2016-01-13 | 지에스칼텍스 주식회사 | Nylon blend composition having improved heat resistance and impact strength and method for preparing the same |
| FR3019040B1 (en) * | 2014-03-31 | 2016-03-11 | Arkema France | COSMETIC COMPOSITION FOR SKIN LIGHTENING |
| WO2017217660A1 (en) * | 2016-06-13 | 2017-12-21 | 연세대학교 산학협력단 | Composition containing suberic acid or salt thereof as active ingredient, and having effects of improving skin moisturization, skin exfoliation, enhancing skin elasticity, inhibiting erythema, alleviating skin wrinkles, or alleviating skin photoaging |
| KR102360818B1 (en) * | 2017-06-30 | 2022-02-09 | (주)아모레퍼시픽 | Water Dispersion Liquid Cosmetic Composition for Eye-makeup |
| KR20190037454A (en) * | 2017-09-29 | 2019-04-08 | (주)아모레퍼시픽 | Priming cosmetic composition and manufacturing method of the same |
| CN110974715B (en) * | 2019-12-26 | 2023-08-01 | 常州纳欧新材料科技有限公司 | APG modified MBBT composite material and preparation method of aqueous slurry thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4610919A (en) * | 1985-06-14 | 1986-09-09 | Fiber Bond Corporation | Binder for fibrous padding |
| DE102004058073A1 (en) * | 2004-12-01 | 2006-06-08 | Basf Ag | Process for the preparation of an aqueous polyamide dispersion |
| WO2006126563A1 (en) * | 2005-05-25 | 2006-11-30 | Toray Industries, Inc. | Polyamide resin fine particles and process for production thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2478465A1 (en) * | 1980-03-18 | 1981-09-25 | Oreal | NEW COSMETIC COMPOSITIONS FOR HAIR, IN TWO LIQUID PHASES, AND THEIR APPLICATION |
| US5874091A (en) * | 1990-09-27 | 1999-02-23 | L'oreal | Cosmetic composition comprising a dispersion of lipid vesicles as well as melanin pigments |
| JP4089852B2 (en) * | 1999-03-01 | 2008-05-28 | 住化エンビロサイエンス株式会社 | Production method of coarse copolymer polyamide fine particles |
| FR2811669A1 (en) * | 2000-07-11 | 2002-01-18 | Atofina | PROCESS FOR THE PREPARATION OF POROUS POWDERS OF COPOLYESTERAMIDES AND POWDERS THUS OBTAINED |
| AU2004251705B2 (en) * | 2003-06-09 | 2007-02-22 | Color Access, Inc. | Stable cosmetic emulsion with polyamide |
| ATE540668T1 (en) * | 2004-10-22 | 2012-01-15 | Oreal | COSMETIC COMPOSITION CONTAINING A POLYORGANOSILOXANE |
| FR2878434B1 (en) * | 2004-11-30 | 2008-03-07 | Arkema Sa | COSMETIC COMPOSITION COMPRISING A FINE AND POROUS POWDER |
| JP4951893B2 (en) * | 2005-08-23 | 2012-06-13 | 東レ株式会社 | Polycaproamide resin fine particles and cosmetics containing the same |
| FR2903595B1 (en) * | 2006-07-11 | 2008-08-22 | Rhodia Recherches & Tech | COSMETIC COMPOSITIONS COMPRISING A THERMOPLASTIC MATERIAL POWDER |
-
2007
- 2007-04-12 FR FR0754431A patent/FR2914856B1/en active Active
-
2008
- 2008-04-14 MX MX2009011000A patent/MX336952B/en active IP Right Grant
- 2008-04-14 KR KR1020097023323A patent/KR101516444B1/en active IP Right Grant
- 2008-04-14 AU AU2008257296A patent/AU2008257296A1/en not_active Abandoned
- 2008-04-14 US US12/595,672 patent/US10463889B2/en active Active
- 2008-04-14 EP EP08788180A patent/EP2134313A2/en not_active Withdrawn
- 2008-04-14 CN CN200880019907.5A patent/CN101677915B/en active Active
- 2008-04-14 RU RU2009141710/15A patent/RU2009141710A/en not_active Application Discontinuation
- 2008-04-14 JP JP2010502556A patent/JP5551580B2/en active Active
- 2008-04-14 WO PCT/FR2008/050662 patent/WO2008145889A2/en active Application Filing
- 2008-04-14 BR BRPI0810537-5A patent/BRPI0810537B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4610919A (en) * | 1985-06-14 | 1986-09-09 | Fiber Bond Corporation | Binder for fibrous padding |
| DE102004058073A1 (en) * | 2004-12-01 | 2006-06-08 | Basf Ag | Process for the preparation of an aqueous polyamide dispersion |
| WO2006126563A1 (en) * | 2005-05-25 | 2006-11-30 | Toray Industries, Inc. | Polyamide resin fine particles and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2914856B1 (en) | 2012-08-03 |
| AU2008257296A1 (en) | 2008-12-04 |
| US10463889B2 (en) | 2019-11-05 |
| KR20100016340A (en) | 2010-02-12 |
| MX2009011000A (en) | 2009-12-11 |
| US20100215701A1 (en) | 2010-08-26 |
| FR2914856A1 (en) | 2008-10-17 |
| CN101677915A (en) | 2010-03-24 |
| MX336952B (en) | 2016-02-03 |
| BRPI0810537B1 (en) | 2021-03-02 |
| WO2008145889A3 (en) | 2009-02-19 |
| JP5551580B2 (en) | 2014-07-16 |
| JP2010523631A (en) | 2010-07-15 |
| EP2134313A2 (en) | 2009-12-23 |
| KR101516444B1 (en) | 2015-05-07 |
| WO2008145889A2 (en) | 2008-12-04 |
| RU2009141710A (en) | 2011-05-20 |
| BRPI0810537A2 (en) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101677915B (en) | Cosmetic composition comprising fine powder | |
| US7700124B2 (en) | Cosmetic compositions comprising a fine and porous powder | |
| US8529918B2 (en) | Water-in oil emulsion foundation comprising a polyol | |
| JP4373141B2 (en) | Water-in-oil emulsion foundation | |
| EP2081544A1 (en) | Skin agent for external use and cosmetic agent including ubiquinone derivative or salt thereof and method using the same | |
| JP2003535883A (en) | Solid emulsion containing liquid fatty phase structured with polymer | |
| WO2008061985A1 (en) | Cosmetic composition comprising at least one aprotic hydrocarbon-based volatile solvent | |
| KR20120027247A (en) | Method for producing free powder particles of polyamide impregnated with at least one cosmetic or pharmaceutical agent, and free powder particles of polyamide having a content of at least 25 wt % of at least one cosmetic or pharmaceutical agent | |
| WO2007020536A2 (en) | Cosmetic method for the targeting of wrinkles | |
| US9211243B2 (en) | Cosmetic composition comprising at least one volatile ester | |
| US20080206292A1 (en) | Cosmetic Method for Targeting of Wrinkles | |
| CN101394895A (en) | Cosmetic composition comprising an oil | |
| US20110150801A1 (en) | Coloured composition for concealing skin imperfections | |
| JP2006509037A (en) | Compositions, in particular cosmetic compositions, comprising at least one alkyl parahydroxybenzoate and at least one lipophilic amino acid derivative | |
| AU2012202501B2 (en) | Cosmetic composition comprising a fine powder | |
| CN101394894A (en) | Cosmetic composition comprising an oil | |
| JP6667996B2 (en) | Cosmetic for makeup and manufacturing method thereof | |
| JP2005002022A (en) | Oil-in-water type emulsion cosmetic | |
| JP2000026239A (en) | Makeup cosmetic | |
| CN101394893A (en) | Cosmetic composition comprising an oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |